Liquid crystalline medium

ABSTRACT

The invention relates to a liquid-crystalline medium comprising at least one compound of the formula I 
                         
in which
 
X,
 
                         
Z 1 , Z 2 , Z 3 , a, b and c are as defined in Claim  1 , and to electro-optical displays containing a liquid-crystalline medium of this type.

The present invention relates to a liquid-crystalline medium, to the use thereof for electro-optical purposes, and to displays containing this medium.

Liquid-crystals are used principally as dielectrics in display devices, since the optical properties of such substances can be modified by an applied voltage. Electro-optical devices based on liquid crystals are extremely well known to the person skilled in the art and can be based on various effects. Examples of such devices are cells having dynamic scattering, DAP (deformation of aligned phases) cells, guest/host cells, TN cells having a twisted nematic structure, STN (supertwisted nematic) cells, SBE (super-birefringence effect) cells and OMI (optical mode interference) cells. The commonest display devices are based on the Schadt-Helfrich effect and have a twisted nematic structure.

The liquid-crystal materials must have good chemical and thermal stability and good stability to electric fields and electromagnetic radiation. Furthermore, the liquid-crystal materials should have low viscosity and produce short addressing times, low threshold voltages and high contrast in the cells.

They should furthermore have a suitable mesophase, for example a nematic or cholesteric mesophase for the above-mentioned cells, at the usual operating temperatures, i.e. in the broadest possible range above and below room temperature. Since liquid crystals are generally used as mixtures of a plurality of components, it is important that the components are readily miscible with one another. Further properties, such as the electrical conductivity, the dielectric anisotropy and the optical anisotropy, have to satisfy various requirements depending on the cell type and area of application. For example, materials for cells having a twisted nematic structure should have positive dielectric anisotropy and low electrical conductivity.

For example, for matrix liquid-crystal displays with integrated non-linear elements for switching individual pixels (MLC displays), media having large positive dielectric anisotropy, broad nematic phases, relatively low birefringence, very high specific resistance, good UV and temperature stability and low vapour pressure are desired.

Matrix liquid-crystal displays of this type are known. Non-linear elements which can be used for individual switching of the individual pixels are, for example, active elements (i.e. transistors). The term “active matrix” is then used, where a distinction can be made between two types:

-   1. MOS (metal oxide semiconductor) or other diodes on a silicon     wafer as substrate. -   2. Thin-film transistors (TFTs) on a glass plate as substrate.

The use of single-crystal silicon as substrate material restricts the display size, since even modular assembly of various part-displays results in problems at the joins.

In the case of the more promising type 2, which is preferred, the electro-optical effect used is usually the TN effect. A distinction is made between two technologies: TFTs comprising compound semiconductors, such as, for example, CdSe, or TFTs based on polycrystalline or amorphous silicon. Intensive work is being carried out world-wide on the latter technology.

The TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counterelectrode on its inside. Compared with the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image. This technology can also be extended to fully color-capable displays, in which a mosaic of red, green and blue filters is arranged in such a way that a filter element is opposite each switchable pixel.

The TFT displays usually operate as TN cells with crossed polarizers in transmission and are illuminated from the back.

The term MLC displays here covers any matrix display with integrated non-linear elements, i.e., besides the active matrix, also displays with passive elements, such as varistors or diodes (MIM=metal-insulator-metal).

MLC displays of this type are particularly suitable for TV applications (for example pocket TVs) or for high-information displays for computer applications (laptops) and in automobile or aircraft construction. Besides problems regarding the angle dependence of the contrast and the response times, difficulties also arise in MLC displays due to insufficiently high specific resistance of the liquid-crystal mixtures [TOGASHI, S., SEKIGUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, September 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, p. 141 ff, Paris; STROMER, M., Proc. Eurodisplay 84, September 1984: Design of Thin Film Transistors for Matrix Addressing of Television Liquid Crystal Displays, p. 145 ff, Paris]. With decreasing resistance, the contrast of an MLC display deteriorates, and the problem of after-image elimination may occur. Since the specific resistance of the liquid-crystal mixture generally drops over the life of an MLC display owing to interaction with the interior surfaces of the display, a high (initial) resistance is very important in order to obtain acceptable service lives. In particular in the case of low-volt mixtures, it was hitherto impossible to achieve very high specific resistance values. It is furthermore important that the specific resistance exhibits the smallest possible increase with increasing temperature and after heating and/or UV exposure. The low-temperature properties of the mixtures from the prior art are also particularly disadvantageous. It is demanded that no crystallisation and/or smectic phases occur, even at low temperatures, and the temperature dependence of the viscosity is as low as possible. The MLC displays from the prior art thus do not meet today's requirements.

In addition to liquid-crystal displays which use back-lighting, i.e. are operated transmissively and if desired transflectively, reflective liquid-crystal displays are also particularly interesting. These reflective liquid-crystal displays use the ambient light for information display. They thus consume significantly less energy than back-lit liquid-crystal displays having a corresponding size and resolution. Since the TN effect is characterised by very good contrast, reflective displays of this type can even be read well in bright ambient conditions. This is already known of simple reflective TN displays, as used, for example, in watches and pocket calculators. However, the principle can also be applied to high-quality, higher-resolution active matrix-addressed displays, such as, for example, TFT displays. Here, as already in the transmissive TFT-TN displays which are generally conventional, the use of liquid crystals of low birefringence (Δn) is necessary in order to achieve low optical retardation (d·Δn). This low optical retardation results in usually acceptable low viewing-angle dependence of the-contrast (cf. DE 30 22 818). In reflective displays, the use of liquid crystals of low birefringence is even more important than in transmissive displays since the effective layer thickness through which the light passes is approximately twice as large in reflective displays as in transmissive displays having the same layer thickness.

There thus continues to be a great demand for MLC displays having very high specific resistance at the same time as a large working-temperature range, short response times even at low temperatures and low threshold voltage which do not have these disadvantages, or only do so to a reduced extent.

In TN (Schadt-Helfrich) cells, media are desired which facilitate the following advantages in the cells:

-   -   extended nematic phase range (in particular down to low         temperatures)     -   the ability to switch at extremely low temperatures (outdoor         use, automobile, avionics)     -   increased resistance to UV radiation (longer service life)     -   low optical birefringence for small layer thicknesses     -   low threshold voltage.

The media available from the prior art do not allow these advantages to be achieved while simultaneously retaining the other parameters.

In the case of supertwisted (STN) cells, media are desired which enable greater multiplexability and/or lower threshold voltages and/or broader nematic phase ranges (in particular at low temperatures). To this end, a further widening of the available parameter latitude (clearing point, smectic-nematic transition or melting point, viscosity, dielectric parameters, elastic parameters) is urgently desired.

The invention has an object of providing media, in particular for MLC, TN or STN displays of this type, which do not have the above-mentioned disadvantages or only do so to a reduced extent, and preferably simultaneously have very high specific resistances and low threshold voltages. This object requires liquid-crystalline compounds which have a high clearing point and low rotational viscosity. Upon further study of the specification and appended claims, further objects and advantages of this invention will become apparent to those skilled in the art.

It has now been found that these and other objects can be achieved if use is made of the liquid-crystalline compound which has a terminal polar radical and a terminal CH₃ group. The compounds of the formula I reduce the elastic constants, in particular K₁, and result in mixtures having particularly low threshold voltages.

The invention thus relates to a liquid-crystalline medium based on a mixture of polar compounds of positive or negative dielectric anisotropy, comprising one or more compounds of the formula

in which

are

-   -   a) a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which         one or two non-adjacent CH₂ groups may be replaced by —O— or         —S—,     -   b) a 1,4-phenylene radical, in which one or two CH groups may be         replaced by N,     -   c) a radical from the group consisting of piperidine-1,4-diyl,         1,4-bicyclo[2.2.2]octylene, naphthalene-2,6-diyl,         decahydronaphthalene-2,6-diyl,         1,2,3,4-tetrahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl         and fluorene-2,7-diyl,     -   where the radicals a), b) and c) may be monosubstituted or         polysubstituted by halogen atoms,

-   x, y and z are each, independently of one another, 0, 1 or 2, -   Z¹, Z² and Z³ are each, independently of one another, —CO—O—,     —O—CO—, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —CH₂CH₂—, —(CH₂)₄)—, —C₂F₄—,     —CH₂CF₂—, —CF₂CH₂—, —CF═CF—, —CH═CH—, —C≡C— or a single bond, -   X is F, Cl, CN, SF₅, NCS, a halogenated or unsubstituted alkyl     radical having up to 8 carbon atoms, in which one or more CH₂ groups     may be replaced by —O— or —CH═CH— in such a way that O atoms are not     linked directly to one another, -   a is 0, 1 or 2, -   b is 0, 1 or 2, and -   c is 0, 1 or 2, where a+b+c is ≦3.

In the pure state, the compounds of the formula I are colorless and generally form liquid-crystalline mesophases in a temperature range which is favorably located for electro-optical use. In particular, the compounds according to the invention are distinguished by their high clearing point and low rotational viscosity values. They are stable chemically, thermally and to light.

in the compounds of the formula I are preferably

X in the compounds of the formula I is preferably F, Cl, CN, NCS, CF₃, SF₅, CF₂H, OCF₃, CH₃, C₂H₅, n—C₃H₇, n—C₄H₉, n—C₅H₁₁, n—C₆H₁₃, n—C₇H₁₅, OCF₂H, OCFHCF₃, OCFHCFH₂, OCFHCF₂H, OCF₂CH₃, OCF₂CFH₂, OCF₂CF₂H, OCF₂CF₂CF₂H, OCF₂CF₂CFH₂, OCFHCF₂CF₃, OCFHCF₂CF₂H, OCFHCFHCF₃, OCH₂CF₂CF₃, OCF₂CF₂CF₃, CF₂CH₂CF₃, CF₂CHFCF₃, OCF₂CFHCFH₂, OCF₂CH₂CF₂H, OCFHCF₂CFH₂, OCFHCFHCF₂H, OCFHCH₂CF₃, OCH₂CFHCF₃, OCH₂CF₂CF₂H, OCF₂CFHCH₃, OCF₂CH₂CFH₂, OCFHCF₂CH₃, OCFHCFHCFH₂, OCFHCH₂CF₃, OCH₂CF₂CFH₂, OCH₂CFHCF₂H, OCF₂CH₂CH₃, OCFHCFHCH₃, OCFHCH₂CFH₂, OCH₂CF₂CH₃, OCH₂CFHCFH₂, OCH₂CH₂CF₂H, OCHCH₂CH₃, OCH₂CFHCH₃, OCH₂CH₂CF₂H, OCClFCF₃, OCClFCClF₂, OCClFCFH₂, OCFHCCl₂F, OCClFCF₂H, OCClFCClF₂, OCF₂CClH₂, OCF₂CCl₂H, OCF₂CCl₂F, OCF₂CClFH, OCF₂CClF₂, OCF₂CF₂CClF₂, OCF₂CF₂CCl₂F, OCClFCF₂CF₃, OCClFCF₂CF₂H, OCClFCF₂CClF₂, OCClFCFHCF₃, OCClFCClFCF₃, OCCl₂CF₂CF₃, OCClHCF₂CF₃, OCH₂CF₂CHFCF₃, OCClFCF₂CF₃, OCClFCClFCF₃, OCF₂CClFCFH₂, OCF₂CF₂CCl₂F, OCF₂CCl₂CF₂H, OCF₂CH₂CClF₂, OCClFCF₂CFH₂, OCFHCF₂CCl₂F, OCClFCFHCF₂H, OCClFCClFCF₂H, OCFHCFHCClF₂, OCClFCH₂CF₃, OCFHCCl₂CF₃, OCCl₂CFHCF₃, OCH₂CClFCF₃, OCCl₂CF₂CF₂H, OCH₂CF₂CClF₂, OCF₂CClFCH₃, OCF₂CFHCCl₂H, OCF₂CCl₂CFH₂, OCF₂CH₂CCl₂F, OCClFCF₂CH₃, OCFHCF₂CCl₂H, OCClFCClFCFH₂, OCFHCFHCCl₂F, OCClFCH₂CF₃, OCFHCCl₂CF₃, OCCl₂CF₂CFH₂, OCH₂CF₂CCl₂F, OCCl₂CFHCF₂H, OCClHCClFCF₂H, OCF₂CClHCClH₂, OCF₂CH₂CCl₂H, OCClFCFHCH₃, OCF₂CClFCCl₂H, OCClFCH₂CFH₂, OCFHCCl₂CFH₂, OCCl₂CF₂CH₃, OCH₂CF₂CClH₂, OCCl₂CFHCFH₂, OCH₂CClFCFCI₂, OCH₂CH₂CF₂H, OCClHCClHCF₂H, OCH₂CCl₂CF₂H, OCClFCH₂CH₃, OCFHCH₂CCl₂H, OCClHCFHCClH₂, OCH₂CFHCCl₂H, OCCl₂CH₂CF₂H, OCH₂CCl₂CF₂H, CH═CF₂, CF═CF₂, OCH═CF₂, OCF═CF₂, CH═CHF, OCH═CHF, CF═CHF, OCF═CHF, in particular F, Cl, CN, NCS, CF₃, C₂F₅,n—C₃F₇, SF₅, CF₂H, OCF₃, OCF₂H, OCFHCF₃, OCFHCFH₂, OCFHCF₂H, OCF₂CH₃, OCF₂CFH₂, OCF₂CF₂H, OCF₂CF₂CF₂H, OCF₂CF₂CFH₂, OCFHCF₂CF₃, OCFHCF₂CF₂H, OCF₂CF₂CF₃, CF₂CHFCF₃, CF₂CH₂CF₃, OCH₂CF₂CHFCF₃, OCF₂CHFCF₃, OCClFCF₂CF₃, CH₃, C₂H₅ and n—C₃H₇.

For reasons of simplicity, Cyc below denotes a 1,4-cyclohexylene radical, Che denotes a 1,4-cyclohexenylene radical, Dio denotes a 1,3-dioxane-2,5-diyl radical, Dit denotes a 1,3-dithiane-2,5-diyl radical, Phe denotes a 1,4-phenylene radical, Pyd denotes a pyridine-2,5-diyl radical, Pyr denotes a pyrimidine-2,5-diyl radical, Bi denotes a bicyclo[2.2.2]octylene radical, PheF denotes a 2- or 3-fluoro-1,4-phenylene radical, PheFF denotes a 2,3-difluoro- or 2,6-difluoro-1,4-phenylene radical, Nap denotes a substituted or unsubstituted naphthalene radical, Dec denotes a decahydronaphthalene radical.

The compounds of the formula I accordingly include the preferred bicyclic compounds of the sub-formulae Ia and Ib: CH₃—A¹—A⁴—X  Ia CH₃—A1—Z¹—A⁴—X  Ib tricyclic compounds of the sub-formulae Ic to If: CH₃—A¹—A²—A⁴—X  Ic CH₃—A¹—Z¹—A²—A⁴—X  Id CH₃—A¹—Z¹—A²—Z²—A⁴—X  Ie CH₃—A¹—A²—Z²—A⁴—X  If tetracyclic compounds of the sub-formulae Ig to Im: CH₃—A¹—A²—A³—A⁴—X  Ig CH₃—A¹—Z¹—A²—A³—A⁴—X  Ih CH₃—A¹—A²—Z²—A³—A⁴—X  Ii CH₃—A¹—A²A³—Z³—A⁴—X  Ij CH₃—A¹—Z¹—A²—Z²—A³—A⁴—X  Ik CH₃—A¹—Z¹—A²—A³—Z³—A⁴—X  Il CH₃—A¹—A²—Z²—A³—Z³—A⁴—X  Im

Of these, particular preference is given to the compounds of the sub-formulae Ic, Id, and Ie.

A¹, A², A³ and A⁴ are preferably Phe, PheF, PheFF, Cyc or Che, furthermore Pyr or Dio, Dec or Nap. The compounds of the formula I preferably contain not more than one of the radicals Bi, Pyd, Pyr, Dio, Dit, Nap or Dec.

Preference is also given to all compounds of the formula I and of all sub-formulae in which A⁴ is a monosubstituted or disubstituted 1,4-phenylene. These are, in particular, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene and 2,6-difluoro-1,4-phenylene.

Preferred smaller subgenus of compounds of the formula I are those of the sub-formulae I1 to I31:

in which X is as defined in Claim 1, and “alkyl” is a straight-chain or branched alkyl radical having 1-8 carbon atoms, and L¹ to L⁶ are each, independently of one another, H or F.

Particularly preferred media comprise one or more compounds selected from the group consisting of the compounds of the formulae

The compounds of the formula I are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for the said reactions. Use can also be made here of variants which are known per se, but are not mentioned here in greater detail. Liquid-crystalline compounds having a CF₂O bridge or C₂F₄ bridge can be prepared, for example, as described in P. Kirsch et al., Angew. Chem. 2001, 113, 1528-1532 or 2001, 123, 5414-5417.

The compounds of the formula I can be prepared, for example, as described in European Patent Specifications 0 334 911, 0 387 032, 0 441 932 and 0 628 532. JP 2000-192040 gives the lipophilicity parameters of a few compounds containing a terminal CH₃ group.

The invention also relates to electro-optical displays (in particular STN or MLC displays having two plane-parallel outer plates, which, together with a frame, form a cell, integrated non-linear elements for switching individual pixels on the outer plates, and a nematic liquid-crystal mixture of positive dielectric anisotropy and high specific resistance which is located in the cell) which contain media of this type, and to the use of these media for electro-optical purposes.

The liquid-crystal mixtures according to the invention enable a significant widening of the available parameter latitude.

The achievable combinations of clearing point, optical anisotropy, viscosity at low temperature, thermal and UV stability and dielectric anisotropy are far superior to previous materials from the prior art.

The requirement for a high clearing point, a nematic phase at low temperature and a high Δ∈ has hitherto only been achieved to an inadequate extent. Although liquid-crystal mixtures such as, for example, MLC-6476 and MLC-6625 (Merck KGaA, Darmstadt, Germany) have comparable clearing points and low-temperature stabilities, they have, however, relatively low Δn values and also higher threshold voltages of about ≧1.7 V.

Other mixture systems have comparable viscosities and Δ∈ values, but only have clearing points in the region of 60° C.

The liquid-crystal mixtures according to the invention, while retaining the nematic phase down to −20° C. and preferably down to −30° C., particularly preferably down to −40° C., enable clearing points above 80° C., preferably above 90° C., particularly preferably above 100° C., simultaneously dielectric anisotropy values Δ∈ of ≧4, preferably ≧6, and a high value for the specific resistance to be achieved, enabling excellent STN and MLC displays to be obtained. In particular, the mixtures are characterised by low operating voltages. The TN thresholds are below 1.5 V, preferably below 1.3 V.

It goes without saying that, through a suitable choice of the components of the mixtures according to the invention, it is also possible for higher clearing points (for example above 110°) to be achieved at a higher threshold voltage or lower clearing points to be achieved at lower threshold voltages with retention of the other advantageous properties. At viscosities correspondingly increased only slightly, it is likewise possible to obtain mixtures having greater Δ∈ and thus lower thresholds. The MLC displays according to the invention preferably operate at the first Gooch and Tarry transmission minimum [C. H. Gooch and H. A. Tarry, Electron. Lett. 10, 2-4, 1974; C. H. Gooch and H. A. Tarry, Appl. Phys., Vol. 8, 1575-1584, 1975] are used, where, besides particularly favorable electro-optical properties, such as, for example, low angle dependence of the contrast (German Patent 30 22 818), a lower dielectric anisotropy is sufficient at the same threshold voltage as in an analogous display at the second minimum. This enables significantly higher specific resistances to be achieved using the mixtures according to the invention at the first minimum than in the case of mixtures comprising cyano compounds. Through a suitable choice of the individual components and their proportions by weight, the person skilled in the art is able to set the birefringence necessary for a pre-specified layer thickness of the MLC display using simple routine methods.

The flow viscosity ν₂₀ at 20° C. is preferably <60 mm²·s⁻¹, particularly preferably <50 mm²·s⁻¹. The nematic phase range is preferably at least 90°, in particular at least 100°. This range preferably extends at least from −30° to +80°.

Measurements of the capacity holding ratio (HR) [S. Matsumoto et al., Liquid Crystals 5, 1320 (1989); K. Niwa et al., Proc. SID Conference, San Francisco, June 1984, p. 304 (1984); G. Weber et al., Liquid Crystals 5, 1381 (1989)] have shown that mixtures according to the invention comprising compounds of the formula I exhibit a significantly smaller decrease in the HR with increasing temperature than, for example, analogous mixtures comprising cyanophenylcyclohexanes of the formula

or esters of the formula

instead of the compounds of the formula I.

The UV stability of the mixtures according to the invention is also considerably better, i.e. they exhibit a significantly smaller decrease in the HR on exposure to UV.

The media according to the invention are preferably based on one or more (preferably one, furthermore two, three or more) compounds of the formula I, i.e. the proportion of these compounds is 5-95%, preferably 10-60% and particularly preferably in the range 15-40%.

The individual compounds of the formulae I to IX and their sub-formulae which can be used in the media according to the invention are either known or they can be prepared analogously to the known compounds.

Preferred embodiments are indicated below:

-   -   Medium additionally comprises one or more compounds selected         from the group consisting of the general formulae II to X:

in which the individual radicals have the following meanings:

-   R⁰ is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each     having from 2 to 12 carbon atoms, -   X⁰ is F, Cl, halogenated alkyl, halogenated alkenyl, halogenated     alkenyloxy or halogenated alkoxy each having up to 8 carbon atoms, -   Z⁰ is —CH═CH—, —C₂H₄—, —CH₂O—, —OCH₂—, —(CH₂)₄—, —C₂F₄—, —CF═CF—,     —CF₂O—, —OCF₂— or —COO—, -   Y¹, Y², -   Y³ and Y⁴ are each, independently of one another, H or F, and -   r is 0 or 1.

The compound of the formula IV is preferably

-   -   In particular, the medium additionally comprises one or more         compounds of the formulae

-   -   -   in which R⁰ and Y² are as defined above.

    -   The medium preferably comprises one, two or three, furthermore         four homologues of the compounds selected from the group         consisting of H1 to H18 (n=2-12):

-   -   The medium additionally comprises one or more dioxanes of the         formula DI and/or DII,

-   -   -   in which R⁰ is as defined above. R⁰ in the compounds of the             formula DI and/or DII is preferably straight-chain alkyl or             alkenyl having 1 to 8 carbon atoms.

    -   The medium additionally comprises one or more compounds selected         from the group consisting of the general formulae XI to XVI:

-   -   -   in which R⁰, X⁰, Y¹, Y², Y³ and Y⁴ are each, independently             of one another, as defined above, X⁰ preferably being F, Cl,             CF₃, OCF₃ or OCHF₂. R⁰ is preferably alkyl, oxaalkyl,             fluoroalkyl, alkenyl or alkenyloxy.

    -   The proportion of compounds of the formulae I to X together in         the mixture as a whole is at least 50% by weight.

    -   The proportion of compounds of the formula I in the mixture as a         whole is from 5 to 50% by weight.

    -   The proportion of compounds of the formulae Il to X in the         mixture as a whole is from 30 to 70% by weight.

-   -   The medium comprises compounds of the formulae II, III, IV, V,         VI, VII, VIII, IX and/or X.     -   R⁰ is straight-chain alkyl or alkenyl having from 2 to 8 carbon         atoms.     -   The medium essentially consists of compounds of the formulae I         to XVI.     -   The medium comprises further compounds, preferably selected from         the following group consisting of the general formulae XVII to         XX:

-   -   -   in which R⁰ and X⁰ are as defined above, and the             1,4-phenylene rings may be substituted by CN, chorine or             fluorine. The 1,4-phenylene rings are preferably             monosubstituted or polysubstituted by fluorine atoms.

    -   The medium comprises further compounds, preferably selected from         the following group consisting of the formulae RI to RXIV:

-   -   -   in which         -   R⁰ is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl,             each having from 2 to 8 carbon atoms,         -   d is 0, 1 or 2,         -   Y¹ is H or F,         -   alkyl and         -   alkyl* are each, independently of one another, a             straight-chain or branched alkyl radical having from 2 to 8             carbon atoms,         -   alkenyl and         -   alkenyl* are each, independently of one another, a             straight-chain or branched alkenyl radical having from 2 to             8 carbon atoms.

    -   The medium preferably comprises one or more compounds of the         formulae

-   -   -   in which n and m are each an integer from 2 to 8.

    -   The I: (II+III+IV+V+VI+VII+VIII+IX+X) weight ratio is preferably         from 1:10 to 10:1.

    -   The medium essentially consists of compounds selected from the         group consisting of the general formulae I to XVI.

It has been found that even a relatively small proportion of compounds of the formula I mixed with conventional liquid-crystal materials, but in particular with one or more compounds of the formulae II, III, IV, V, VI, VII, VIII, IX and/or X, results in a significant lowering of the threshold voltage and in low birefringence values, with broad nematic phases with low smectic-nematic transition temperatures being observed at the same time, improving the shelf life. The compounds of the formulae I to X are colorless, stable and readily miscible with one another and with other liquid-crystalline materials.

The term “alkyl” or “alkyl*” covers straight-chain and branched alkyl groups having from 2 to 8 carbon atoms, in particular the straight-chain groups ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having 2-5 carbon atoms are generally preferred.

The term “alkenyl” or “alkenyl*”covers straight-chain and branched alkenyl groups having up to 8 carbon atoms, in particular the straight-chain groups. Preferred alkenyl groups are C₂-C₇-1E-alkenyl, C₄-C₇-3E-alkenyl, C₅-C₇-4-alkenyl, C₆-C₇-5-alkenyl and C₇-6-alkenyl, in particular C₂-C₇-1E -alkenyl, C₄-C₇-3E-alkenyl and C₅-C₇-4-alkenyl. Examples of particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.

The term “fluoroalkyl” preferably covers straight-chain groups having a terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other positions of the fluorine are not excluded.

The term “oxaalkyl” preferably covers straight-chain radicals of the formula C_(n)H_(2n+1)—O—(CH₂)_(m), in which n and m are each, independently of one another, from 1 to 6. n is preferably=1 and m is preferably from 1 to 6.

Through a suitable choice of the meanings of R⁰ and X⁰, the addressing times, the threshold voltage, the steepness of the transmission characteristic lines, etc., can be modified in the desired manner. For example, 1E-alkenyl radicals, 3E-alkenyl radicals, 2E-alkenyloxy radicals and the like generally result in shorter addressing times, improved nematic tendencies and a higher ratio of the elastic constants k₃₃ (bend) and k₁₁ (splay) compared with alkyl or alkoxy radicals. 4-alkenyl radicals, 3-alkenyl radicals and the like generally give lower threshold voltages and larger values of k₃₃/k₁₁ compared with alkyl and alkoxy radicals.

A —CH₂CH₂— group in Z¹ generally results in higher values of k₃₃/k₁₁ compared with a single covalent bond. Higher values of k₃₃/k₁₁ facilitate, for example, flatter transmission characteristic lines in TN cells with a 90° twist (in order to achieve grey shades) and steeper transmission characteristic lines in STN, SBE and OMI cells (greater multiplexability), and vice versa.

The optimum mixing ratio of the compounds of the formulae I and II+III+IV+V+VI+VII+VIII+IX+X depends substantially on the desired properties, on the choice of the components of the formulae I, II, III, IV, V, VI, VII, VIII, IX and/or X, and the choice of any other components that may be present. Suitable mixing ratios within the range given above can easily be determined from case to case.

The total amount of compounds of the formulae I to XVI in the mixtures according to the invention is not crucial. The mixtures can therefore comprise one or more further components for the purposes of optimising various properties. However, the observed effect on the addressing times and the threshold voltage is generally greater, the higher the total concentration of compounds of the formulae I to XVI.

In a particularly preferred embodiment, the media according to the invention comprise compounds of the formulae II to X (preferably II and/or III) in which X⁰ is OCF₃, OCHF₂, F, OCH═CF₂, OCF═CF₂, OCF₂CHFCF₃ or OCF₂—CF₂H. A favorable synergistic effect with the compounds of the formula I results in particularly advantageous properties.

The mixtures according to the invention having low optical anisotropy (Δn<0.07) are particularly suitable for reflective displays. Low V_(th) mixtures are particularly suitable for 2.5 V and 3.3 V drivers and 4V- or 5V drivers. Ester-free mixtures are preferred for the latter applications.

The construction of the MLC display according to the invention from polarizers, electrode base plates and surface-treated electrodes corresponds to the conventional construction for displays of this type. The term “conventional construction” is broadly drawn here and also covers all derivatives and modifications of the MLC display, in particular including matrix display elements based on poly-Si TFT or MIM.

A significant difference between the displays according to the invention and the conventional displays based on the twisted nematic cell consists, however, in the choice of the liquid-crystal parameters of the liquid-crystal layer.

The liquid-crystal mixtures which can be used in accordance with the invention are prepared in a manner conventional per se. In general, the desired amount of the components used in the lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after thorough mixing.

The dielectrics may also comprise further additives known to the person skilled in the art and described in the literature. For example, 0-15% of pleochroic dyes or chiral dopants can be added.

The entire disclosures of all applications, patents and publications, cited herein and of corresponding German application No. 10150198.6, filed Oct. 12, 2001 are incorporated by reference herein.

Herein, C denotes a crystalline phase, S a smectic phase, S_(c) a smectic C phase, N a nematic phase and I the isotropic phase.

V₁₀ denotes the voltage for 10% transmission (viewing angle perpendicular to the plate surface). t_(on) denotes the switch-on time and t_(off) the switch-off time at an operating voltage corresponding to 2 times the value of V₁₀. Δn denotes the optical anisotropy and n_(o) the refractive index. Δ∈ denotes the dielectric anisotropy.(Δ∈=∈_(∥)−∈_(⊥), where ∈_(∥) denotes the dielectric constant parallel to the longitudinal molecular axes and ∈_(⊥) denotes the dielectric constant perpendicular thereto). The electro-optical data are measured in a TN cell at the 1st minimum (i.e. at a d·Δn value of 0.5) at 20° C., unless expressly stated otherwise. The optical data are measured at 20° C., unless expressly stated otherwise.

In the present application and in the examples below, the structures of the liquid-crystal compounds are indicated by means of acronyms, the transformation into chemical formulae taking place in accordance with Tables A and B below. All radicals C_(n)H_(2n+1) and C_(m)H_(2m+1) are straight-chain alkyl radicals having n and m carbon atoms respectively; n and m are in each case, independently of one another, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15. The coding in Table B is self-evident. In Table A, only the acronym for the parent structure is indicated. In individual cases, the acronym for the parent structure is followed, separated by a dash, by a code for the substituents R¹, R², L¹ and L²:

Code for R¹, R², L¹, L² R¹ R² L¹ L² nm C_(n)H_(2n+1) C_(m)H_(2m+1) H H nOm C_(n)H_(2n+1) OC_(m)H_(2m+1) H H nO.m OC_(n)H_(2n+1) C_(m)H_(2m+1) H H n C_(n)H_(2n+1) CN H H nN•F C_(n)H_(2n+1) CN H F nF C_(n)H_(2n+1) F H H nOF OC_(n)H_(2n+1) F H H nCl C_(n)H_(2n+1) Cl H H nF•F C_(n)H_(2n+1) F H F nF•F•F C_(n)H_(2n+1) F F F nCF₃ C_(n)H_(2n+1) CF₃ H H nOCF₃ C_(n)H_(2n+1) OCF₃ H H nOCF₂ C_(n)H_(2n+1) OCHF₂ H H nS C_(n)H_(2n+1) NCS H H rVsN C_(r)H_(2r+1)—CH═CH—C_(s)H_(2s)— CN H H rEsN C_(r)H_(2r+1)—O—C₂H_(2s)— CN H H nAm C_(n)H_(2n+1) COOC_(m)H_(2m+1) H H nOCCF₂•F•F C_(n)H_(2n+1) OCH₂CF₂H F F

Preferred mixture components are given in Tables A and B.

TABLE A

PYP

PYRP

BCH

CBC

CCH

CCP

CPTP

CEPTP

ECCP

CECP

EPCH

PCH

PTP

BECH

EBCH

CPC

B

FET-nF

CGG

CGU

CUP

CCQU

CWCQU

PUQU

TABLE B

CBC-nmF

PCH-nOm

FET-nCl

CP-nOCF₃

CCH-nOm

BCH-n.FX

Inm

CBC-nmF

ECCP-nm

CCH-n1EM

T-nFm

CGU-n-F

CCP-nOCF₃.F

CGG-n-F

CCP-nOCF₂.F(.F)

CCP-nF.F.F

CGU-n-OXF

CUZU-n-F

CGU-n-O1DT

CCZU-n-F

CC-n-V1

CC-n-V

CCP-nOCF₃

BCH-nF.F.F

CWCZU-n-F

CWCZG-n-F

CCOC-n-m

CGZU-n-F

CUZP-n-F

CGU-1V-F

CCG-V-F

CGZP-n-F

UZP-n-N

CGZP-n-OT

CUZP-n-OT

CCQU-n-F

Dec-U-n-F

Nap-U-n-F

CWGZG-n-F

CWCZG-n-OT

CWCZP-n-OT

CWCQU-n-F

CCP-nF.F

TABLE C Table C shows possible dopants which are generally added to the mixtures according to the invention.

C 15

CB 15

CM 21

R/S-811

CM 44

CM 45

CM 47

CN

R/S-1011

R/S-2011

R/S-3011

R/S-4011

TABLE D Stabilisers which can be added, for example, to the mixtures according to the invention are indicated below.

EXAMPLES

The following examples are intended to explain the invention without restricting it. Above and below, percentages are percent by weight. All temperatures are given in degrees Celsius. m.p. denotes melting point, cl.p. denotes clearing point. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The data between these symbols represent the transition temperatures. Δn denotes optical anisotropy (589 nm, 20° C.), the flow viscosity ν₂₀ (mm²/sec) is determined at 20° C. The rotational viscosity γ₁ [mPa·s] is likewise determined at 20° C.

Mixture Examples

Example M1 CCP-2F•F•F 10.00% S → N [° C.]: <−40 CCP-3F•F•F 10.00% Clearing point [° C.]: 82.0 CCP-10CF₃•F 13.00% Δn [589 nm, 20° C.]: 0.0924 CCP-20CF₃•F 11.00% γ₁ [mPa · s, 20° C.]: 169 CCP-30CF₃•F 8.00% d · Δn [μm]: 0.5 CCP-20CF₃ 8.00% Twist [°]: 90 CCP-30CF₃ 7.00% V_(10,0,20) [V]: 1.24 CCP-40CF₃ 4.00% CGU-2-F 10.00% CGU-3-F 9.50% CGU-5-F 1.00% CCG-V-F 1.50% CCGU-3-F 4.50% BCH-32 2.50% Example M2 CCP-2F•F•F 9.50% CCP-3F•F•F 10.50% CCP-10CF₃•F 13.00% CCP-20CF₃•F 12.00% CCP-30CF₃•F 6.00% CCP-20CF₃ 8.00% CCP-30CF₃ 7.00% CCP-40CF₃ 4.00% CGU-2-F 10.00% CGU-3-F 10.00% CCG-V-F 3.00% CCGU-3-F 3.00% BCH-32 4.00% Example M3 CCP-2F•F•F 9.00% S → N [° C.]: <−40 CCP-3F•F•F 9.00% Clearing point [° C.]: 83.0 CCP-10CF₃•F 12.00% Δn [589 nm, 20° C.]: 0.0938 CCP-20CF₃•F 6.00% γ₁ [mPa · s, 20° C.]: 168 CCP-30CF₃•F 11.00% d · Δn [μm]: 0.5 CCP-20CF₃ 8.00% Twist [°]: 90 CCP-30CF₃ 7.00% V_(10,0,20) [V]: 1.25 CCP-40CF₃ 6.00% CGU-2-F 10.00% CGU-3-F 10.00% CGU-5-F 4.50% CCG-V-F 1.00% CCGU-3-F 3.50% CCP-V-1 3.00% Example M4 CC-3-V 8.00% Clearing point [° C.]: 76.0 CCP-2F•F•F 10.00% Δn [589 nm, 20° C.]: 0.0879 CCP-20CF₃•F 7.50% γ₁ [mPa · s, 20° C.]: 148 CCP-30CF₃ 3.50% d · Δn [μm]: 0.5 CCZU-1-F 10.00% Twist [°]: 90 CCZU-2-F 4.00% V_(10,0,20) [V]: 0.89 CCZU-3-F 15.00% CCZU-5-F 5.00% CGZP-2-OT 11.00% CGZP-3-OT 9.00% CGU-2-F 9.00% CGU-3-F 8.00% Example M5 CC-3-V 18.00% S → N [° C.]: <−30 CCP-2F•F•F 6.00% Clearing point [° C.]: 70.0 CCP-3F•F•F 6.00% Δn [589 nm, 20° C.]: 0.0762 CCZU-1-F 8.00% Δε [kHz, 20° C.]: 11.5 CCZU-2-F 4.00% K₁ [pN, 20° C.]: 8.7 CCZU-3-F 15.00% γ₁ [mPa · s, 20° C.]: 107 CGU-2-F 3.00% d · Δn [μm]: 0.50 CGZP-2-OT 11.00% Twist [°]: 90 CGZP-3-OT 8.00% CDU-2-F 9.00% CDU-3-F 9.00% CDU-5-F 3.00% Example M6 PGU-2-F 7.00% Clearing point [° C.]: 76.0 PGU-3-F 4.00% Δn [589 nm, 20° C.]: 0.0920 CGZP-2-OT 8.00% γ₁ [mPa · s, 20° C.]: 78 CGZP-3-OT 3.00% d · Δn [μm]: 0.50 CCZU-1-F 9.00% Twist [°]: 90 CCZU-2-F 4.00% V_(10,0,20) [V]: 1.55 CCP-2F•F•F 8.00% CCP-20CF₃ 5.00% CCP-30CF₃ 6.00% CCG-V-F 5.00% CC-3-V1 12.00% CC-5-V 14.00% CCH-35 5.00% PCH-302 7.50% BCH-32 2.50% Example M7 CC-3-V 6.00% CCP-2F•F•F 9.00% CCP-3F•F•F 7.00% CCP-20CF₃•F 10.00% CCP-30CF₃ 4.00% CCZU-1-F 8.00% CCZU-2-F 3.00% CCZU-3-F 14.00% CCZU-5-F 4.00% CGZP-2-OT 10.00% CGZP-3-OT 8.00% CGU-2-F 9.00% CGU-3-F 8.00% Example M8 CCP-2F•F•F 10.00% Clearing point [° C.]: 82.5 CCP-3F•F•F 10.00% Δn [589 nm, 20° C.]: 0.0945 CCP-20CF₃•F 11.00% γ₁ [mPa · s, 20° C.]: 177 CCP-30CF₃•F 11.00% d · Δn [μm]: 0.50 CCP-50CF₃•F 5.00% Twist [°]: 90 CCP-30CF₃ 8.00% V_(10,020) [V]: 1.29 CCP-40CF₃ 6.00% CCP-50CF₃ 8.00% CGU-1-F 8.00% CGU-2-F 10.00% CGU-3-F 9.00% CCGU-3-F 4.00% Example M9 CCP-2F•F•F 10.00% S → N [° C.]: <−30 CCP-20CF₃ 3.00% Clearing point [° C.]: 74.5 CCP-30CF₃ 8.00% Δn [589 nm, 20° C.]: 0.0874 CCP-40CF₃ 6.00% γ₁ [mPa · s, 20° C.]: 155 CCP-20CF₃•F 8.50% d · Δn [μm]: 0.5 CCZU-2-F 5.00% Twist [°]: 90 CCZU-3-F 15.00% V_(10,0,20) [V]: 1.07 CCZU-5-F 5.00% CGZP-2-OT 9.00% CGZP-3-OT 7.00% CCH-3CF₃ 5.00% CGU-1-F 8.50% CGU-2-F 10.00% Example M10 CC-3-V 18.00% S → N [° C.]: <−30 CCP-20CF₃ 4.00% Clearing point [° C.]: 70.0 CCP-2F•F•F 6.00% Δn [589 nm, 20° C.]: 0.0770 CCZU-2-F 4.00% Δε [kHz, 20° C.]: 11.3 CCZU-3-F 15.00% K₁ [pN, 20° C.]: 8.8 CCZU-5-F 4.00% γ₁ [mPa · s, 20° C.]: 110 CGU-1-F 8.00% d · Δn [μm]: 0.5 CGZP-2-OT 9.00% Twist [°]: 90 CGZP-3-OT 6.00% CDU-2-F 9.00% CDU-3-F 9.00% CDU-5-F 7.00% CCPC-33 1.00% Example M11 CCP-1F•F•F 12.00% S → N [° C.]: <−40 CCP-2F•F•F 10.00% Clearing point [° C.]: 81.0 CCP-3F•F•F 10.00% Δn [589 nm, 20° C.]: 0.0915 CCP-20CF₃•F 11.00% γ₁ [mPa · s, 20° C.]: 163 CCP-30CF₃•F 7.00% d · Δn [μm]: 0.5 CCP-20CF₃ 8.00% Twist [°]: 90 CCP-30CF₃ 3.00% V_(10,0,20) [V]: 1.27 CCP-40CF₃ 7.00% CGU-2-F 10.00% CGU-3-F 10.00% CCG-V-F 4.50% CCGU-3-F 5.00% CBC-33 2.50% Example M12 CC-3-V1 9.00% CC-5-V 3.00% CCH-35 5.00% CCP-1F•F•F 2.50% CCP-2F•F•F 10.00% CGU-2-F 9.00% PGU-2-F 9.00% PGU-3-F 9.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 6.00% CCP-20CF₃•F 9.00% CCP-30CF₃•F 8.50% CCGU-3-F 4.00% Example M13 CCP-1F•F•F 11.00% S → N [° C.]: <−40 CCP-2F•F•F 10.00% Clearing point [° C.]: 81.0 CCP-3F•F•F 10.00% Δn [589 nm, 20° C.]: 0.0928 CCP-20CF₃•F 11.00% Δε [kHz, 20° C.]: 10.0 CCP-30CF₃•F 8.00% K₁ [pN, 20° C.]: 9.0 CCP-20CF₃ 8.00% γ₁ [mPa · s, 20° C.]: 164 CCP-30CF₃ 7.00% d · Δn [μm]: 0.05 CCP-40CF₃ 4.00% Twist [°]: 90 CGU-2-F 10.00% V_(10,0,20) [V]: 1.29 CGU-3-F 9.50% CGU-5-F 1.00% CCG-V-F 2.50% CCGU-3-F 4.00% CBC-33 2.00% BCH-32 2.00% Example M14 CCP-1F•F•F 11.00% CCP-2F•F•F 3.00% CCZU-3-F 13.00% CCP-30CF₃ 8.00% CCP-40CF₃ 2.00% CGZP-2-OT 4.00% PGU-2-F 6.00% PGU-3-F 5.00% CCG-V-F 3.00% CC-5-V 10.00% CC-3-V1 12.00% CCH-35 5.00% CC-3-V 18.00% Example M15 CCP-1F•F•F 10.00% S → N [° C.]: <−40 CCP-2F•F•F 8.00% Clearing point [° C.]: 76.0 CCZU-3-F 13.00% Δn [589 nm, 20° C.]: 0.0782 CCP-30CF₃ 8.00% γ₁ [mPa · s, 20° C.]: 65 CCP-40CF₃ 3.30% d · Δn [μm]: 0.5 CGZP-2-OT 6.00% Twist [°]: 90 PGU-2-F 7.00% V_(10,0,20) [V]: 1.69 CC-5-V 9.00% CC-3-V1 12.00% CCH-35 5.00% CC-3-V 18.00% CBC-33 0.70% Example M16 CC-3-V 8.00 CCP-30CF₃ 1.00 CCP-20CF₃•F 14.00 CCP-2F•F•F 9.00 CGU-2-F 9.00 PGU-2-F 4.00 CCZU-2-F 4.00 CCZU-3-F 15.00 CCZU-5-F 4.00 CGZP-2-OT 11.00 CGZP-3-OT 8.00 CCP-1F•F•F 12.00 CCGU-3-F 1.00 Example M17 CCP-2F•F•F 10.00% Clearing point [° C.]: 75.5 CCZU-2-F 3.00% Δn [589 nm, 20° C.]: 0.0790 CCZU-3-F 14.00% d · Δn [μm]: 0.5 CCP-30CF₃ 6.00% Twist [°]: 90 CGZP-1-OT 11.00% V_(10,0,20) [V]: 1.75 PGU-2-F 6.00% CC-5-V 12.00% CC-3-V1 9.00% CCH-35 5.00% CC-3-V 17.00% CCP-V-1 2.00% PCH-302 4.00% CCOC-3-3 1.00% Example M18 CCP-20CF₃ 3.00% CCP-30CF₃ 7.00% PGU-2-F 8.00% PGU-3-F 6.00% CGZP-1-OT 15.00% CGZP-2-OT 8.00% CGZP-3-OT 7.00% CCZU-2-F 4.00% CCZU-3-F 8.00% CC-5-V 15.00% CC-3-V1 9.00% CCH-35 4.00% PCH-53 6.00% Example M19 PGU-2-F 6.70% Clearing point [° C.]: 74.0 CGZP-1-OT 12.00% Δn [589 nm, 20° C.]: 0.0919 CGZP-2-OT 8.00% d · Δn [μm]: 0.5 CGZP-3-OT 5.00% Twist [°]: 90 CCP-2F•F•F 4.00% V_(10,0,20) [V]: 1.59 CCZU-2-F 3.00% CCZU-3-F 12.00% CC-3-V1 9.00% CC-5-V 15.00% CCH-35 4.00% CCP-V-1 5.00% PCH-302 12.00% PCH-7F 4.30% Example M20 CCP-20CF₃ 3.00% CCP-30CF₃ 7.00% PGU-2-F 8.00% PGU-3-F 8.00% CGZP-1-OT 12.00% CGZP-2-OT 8.00% CGZP-3-OT 7.00% CCZU-2-F 4.00% CCZU-3-F 9.00% CC-5-V 15.00% CC-3-V1 9.00% CCH-35 5.00% PCH-53 5.00% Example M21 CC-3-V 20.00% S → N [° C.]: <−30 CCP-2F•F•F 6.00% Clearing point [° C.]: 69.0 CCP-3F•F•F 5.00% Δn [589 nm, 20° C.]: 0.0775 CCZU-2-F 4.00% Δε [kHz, 20° C.]: 11.0 CCZU-3-F 14.00% K₁ [pN, 20° C.]: 8.6 CCZU-5-F 4.00% d · Δn [μm]: 0.5 CGU-2-F 5.00% Twist [°]: 90 CGZP-1-OT 7.00% CGZP-2-OT 7.00% CGZP-3-OT 6.00% CDU-2-F 9.00% CDU-3-F 9.00% CDU-5-F 4.00% Example M22 CC-3-V 20.00% S → N [° C.]: <−30 CCP-2F•F•F 9.00% Clearing point [° C.]: 71.0 CCZU-2-F 3.00% Δn [589 nm, 20° C.]: 0.0772 CCZU-3-F 11.00% Δε [kHz, 20° C.]: 10.9 CGZP-1-OT 10.00% K₁ [pN, 20° C.]: 9.8 CGZP-2-OT 10.00% γ₁ [mPa · s, 20° C.]: 100 CGZP-3-OT 5.00% d · Δn [μm]: 0.5 CDU-2-F 9.00% Twist [°]: 90 CDU-3-F 9.00% V_(10,0,20) [V]: 1.0 CDU-5-F 9.00% CCH-35 4.00% Example M23 CCP-1F•F•F 15.00% CCP-2F•F•F 15.00% CCP-3F•F•F 14.00% CCP-4F•F•F 17.00% CCP-5F•F•F 16.00% CCP-6F•F•F 17.00% CCOC-3-3 3.00% CCOC-4-3 3.00% Example M24 CCP-1F•F•F 12.00% S → N [° C.]: <−40 CCP-2F•F•F 10.00% Clearing point [° C.]: 81.0 CCP-3F•F•F 10.00% Δn [589 nm, 20° C.]: 0.0915 CCP-20CF₃•F 11.00% γ₁ [mPa · s, 20° C.]: 163 CCP-30CF₃•F 7.00% d · Δn [μm]: 0.5 CCP-20CF₃ 8.00% Twist [°]: 90 CCP-30CF₃ 3.00% V_(10,0,20) [V]: 1.27 CCP-40CF₃ 7.00% CGU-2-F 10.00% CGU-3-F 10.00% CCG-V-F 4.50% CCGU-3-F 5.00% CBC-33 2.50% Example M25 CCP-1F•F•F 12.00% CCP-2F•F•F 10.00% CCP-3F•F•F 11.00% CCP-20CF₃•F 11.00% CCP-30CF₃•F 3.00% CCP-20CF₃ 8.00% CCP-30CF₃ 7.00% CCP-40CF₃ 7.00% CGU-2-F 10.00% CGU-3-F 10.00% CCG-V-F 1.00% BCH-2F•F 2.00% CCGU-3-F 5.00% CBC-33 3.00% Example M26 CCP-1F•F•F 14.00% Clearing point [° C.]: 81.5 CCP-2F•F•F 13.00% Δn [589 nm, 20° C.]: 0.0703 CCP-3F•F•F 12.00% d · Δn [μm]: 0.5 CCP-4F•F•F 13.00% Twist [°]: 90 CCP-5F•F•F 11.00% V_(10,0,20) [V]: 1.41 CCP-6F•F•F 14.00% CCP-7F•F•F 12.00% CCOC-3-3 3.00% CCOC-4-3 3.00% CCOC-3-5 2.00% CCH-3CF₃ 3.00% Example M27 CCP-1F•F•F 16.00% Clearing point [° C.]: 81.5 CCP-2F•F•F 15.00% Δn [589 nm, 20° C.]: 0.0714 CCP-3F•F•F 14.00% d · Δn [μm]: 0.5 CCP-4F•F•F 19.00% Twist [°]: 90 CCP-5F•F•F 15.00% V_(10,0,20) [V]: 1.37 CCP-7F•F•F 15.00% CCOC-3-3 3.00% CCOC-4-3 3.0% Example M28 CC-5-V 10.00% CC-3-V1 12.00% CCH-35 4.00% CC-3-V 18.00% CCP-1F•F•F 12.00% CCP-2F•F•F 10.00% CCZU-3-F 6.00% CCP-30CF₃ 7.00% CGZP-2-OT 11.00% CGZP-3-OT 4.00% PGU-2-F 3.00% CBC-33 3.00% Example M29 CCP-1F•F•F 12.00% S → N [° C.]: <−40 CCP-2F•F•F 11.00% Clearing point [° C.]: 85.5 CCP-3F•F•F 11.00% Δn [589 nm, 20° C.]: 0.0924 CCP-20CF₃•F 11.00% d · Δn [μm]: 0.5 CCP-20CF₃ 8.00% Twist [°]: 90 CCP-30CF₃ 8.00% V_(10,0,20) [V]: 1.45 CCP-40CF₃ 2.00% CCG-V-F 15.00% CGU-2-F 3.00% BCH-3F•F•F 11.00% BCH-32 5.00% CCP-V-1 2.00% CBC-33 1.00% Example M30 CC-5-V 15.00% S → N [° C.]: <−40 CCH-35 5.00% Clearing point [° C.]: 69.5 CCH-3CF₃ 3.00% Δn [589 nm, 20° C.]: 0.0768 CCP-1F•F•F 12.00% Δε [kHz, 20° C.]: 9.2 CCP-2F•F•F 10.00% K₁ [pN, 20° C.]: 8.9 CCP-3F•F•F 10.00% γ₁ [mPa · s, 20° C.]: 102 CGU-2-F 9.00% d · Δn [μm]: 0.5 CGZP-2-OT 11.00% Twist [°]: 90 CGZP-3-OT 2.00% V_(10,0,20) [V]: 1.04 CCZU-2-F 4.00% CCZU-3-F 15.00% CCP-20CF₃ 2.00% CBC-33 2.00% Example M31 CC-3-V1 9.00% S → N [° C.]: <−40 CC-5-V 12.00% Clearing point [° C.]: 79.0 CCH-35 4.00% Δn [589 nm, 20° C.]: 0.0929 PGU-2-F 9.00% γ₁ [mPa · s, 20° C.]: 93 CGZP-2-OT 9.00% d · Δn [μm]: 0.5 BCH-3F•F•F 7.00% Twist [°]: 90 CCP-1F•F•F 11.00% V_(10,0,20) [V]: 1.43 CCP-2F•F•F 10.00% CCP-40CF₃ 7.00% CCP-30CF₃ 8.00% CCZU-2-F 4.00% CCZU-3-F 7.00% BCH-32 3.00% Example M32 CC-3-V1 9.00% S → N [° C.]: <−40 CGU-2-F 10.00% Clearing point [° C.]: 79.0 CGU-3-F 10.00% Δn [589 nm, 20° C.]: 0.0941 BCH-3F•F•F 10.00% γ₁ [mPa · s, 20° C.]: 121 CCP-1F•F•F 11.00% d · Δn [μm]: 0.5 CCP-2F•F•F 10.00% Twist [°]: 90 CCP-3F•F•F 9.00% V_(10,0,20) [V]: 1.40 CCP-30CF₃ 8.00% CCP-40CF₃ 8.00% CCP-50CF₃ 3.00% CCP-V-1 12.00% Example M33 CC-3-V 10.00% CCP-30CF₃ 5.00% CCP-2F•F•F 11.00% CGU-2-F 11.00% PGU-2-F 5.00% CCZU-2-F 5.00% CCZU-3-F 15.00% CCZU-5-F 5.00% CGZP-2-OT 11.00% CGZP-3-OT 9.00% CCP-1F•F•F 12.00% CCH-35 1.00% Example M34 CC-3-V 7.00% Clearing point [° C.]: 81.0 CCP-30CF₃ 3.00% Δn [589 nm, 20° C.]: 0.0878 CCP-20CF₃•F 9.00% Δε [kHz, 20° C.]: 11.9 CCP-2F•F•F 11.00% γ₁ [mPa · s, 20° C.]: 136 CGU-2-F 10.00% d · Δn [μm]: 0.5 PGU-2-F 4.00% Twist [°]: 90 CCZU-2-F 5.00% V_(10,0,20) [V]: 0.98 CCZU-3-F 15.00% CCZU-5-F 4.00% CGZP-2-OT 11.00% CGZP-3-OT 9.00% CCP-1F•F•F 12.00% Example M35 CCH-35 5.00% S → N [° C.]: <−40 CCH-3CF₃ 6.00% Clearing point [° C.]: 69.5 CCP-20CF₃ 8.00% Δn [589 nm, 20° C.]: 0.0896 CCP-30CF₃ 8.00% γ₁ [mPa · s, 20° C.]: 130 CCP-1F•F•F 12.00% d · Δn [μm]: 0.5 CCP-2F•F•F 6.00% Twist [°]: 90 CGU-2-F 11.00% V_(10,0,20) [V]: 1.07 CCZU-2-F 5.00% CCZU-3-F 15.00% CCZU-5-F 4.00% PGU-2-F 8.00% CGZP-2-OT 10.00% CBC-33 2.00% Example M36 CCP-1F•F•F 10.00% CCP-2F•F•F 4.00% CCZU-2-F 4.00% CCZU-3-F 13.00% CCP-30CF₃ 8.00% CGZP-2-OT 10.00% PGU-2-F 5.00% CC-5-V 11.00% CC-3-V1 11.00% CCH-35 4.50% CC-3-V 18.00% CBC-33 1.50% Example M37 CCP-1F•F•F 11.00% S → N [° C.]: <−20 CCZU-2-F 4.00% Clearing point [° C.]: 77.5 CCZU-3-F 13.00% Δn [589 nm, 20° C.]: 0.0773 CCP-30CF₃ 8.00% γ₁ [mPa · s, 20° C.]: 63 CGZP-2-OT 11.00% d · Δn [μm]: 0.5 PGU-2-F 5.00% Twist [°]: 90 CC-5-V 12.00% V_(10,0,20) [V]: 1.80 CC-3-V1 11.00% CCH-35 4.00% CC-3-V 18.00% CCP-V-1 3.00% Example M38 CC-5-V 12.00% S → N [° C.]: <−20 CC-3-V1 11.00% Clearing point [° C.]: 77.0 CCH-35 5.00% Δn [589 nm, 20° C.]: 0.0773 CC-3-V 18.00% Δε [kHz, 20° C.]: 6.0 CCH-3CF₃ 2.00% γ₁ [mPa · s, 20° C.]: 63 CCP-1F•F•F 10.50% d · Δn [μm]: 0.5 CCZU-3-F 11.50% Twist [°]: 90 CCP-30CF₃ 8.00% V_(10,0,20) [V]: 1.84 CGZP-2-OT 10.50% CGZP-3-OT 5.50% PGU-2-F 4.00% CCP-V-1 2.00% Example M39 CCP-1F•F•F 12.00% S → N [° C.]: <−40 CCP-2F•F•F 6.50% Clearing point [° C.]: 80.0 CCP-20CF₃•F 11.00% Δn [589 nm, 20° C.]: 0.0930 CCP-30CF₃•F 11.00% d · Δn [μm]: 0.5 CCP-20CF₃ 8.00% Twist [°]: 90 CCP-30CF₃ 8.00% V_(10,0,20) [V]: 1.32 CCP-40CF₃ 8.00% CCP-50CF₃ 7.50% CGU-2-F 10.50% CGU-3-F 9.00% CBC-33 1.50% BCH-3F•F•F 7.00% Example M40 CCP-1F•F•F 12.00% CCP-2F•F•F 11.00% CCP-3F•F•F 11.00% CCP-20CF₃•F 11.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 8.00% CCG-V-F 15.00% CGU-2-F 3.00% BCH-3F•F•F 8.00% BCH-32 3.00% CCP-V-1 2.00% Example M41 CC-3-V 10.00% Clearing point [° C.]: 69.0 CCP-30CF₃ 5.00% Δn [589 nm, 20° C.]: 0.0875 CCP-20CF₃•F 2.00% Δε [kHz, 20° C.]: 12.2 CCP-2F•F•F 11.00% γ₁ [mPa · s, 20° C.]: 124 CGU-2-F 11.00% d · Δn [μm]: 0.5 PGU-2-F 4.00% Twist [°]: 90 CCZU-2-F 5.00% V_(10,0,20) [V]: 1.02 CCZU-3-F 15.00% CCZU-5-F 5.00% CGZP-2-OT 11.00% CGZP-3-OT 9.00% CCP-1F•F•F 12.00% Example M42 CCP-1F•F•F 12.00% S → N [° C.]: <−40 CCP-2F•F•F 11.00% Clearing point [° C.]: 83.0 CCP-3F•F•F 11.00% Δn [589 nm, 20° C.]: 0.0932 CCP-20CF₃•F 11.00% γ₁ [mPa · s, 20° C.]: 160 CCP-30CF₃•F 5.00% d · Δn [μm]: 0.5 CCP-20CF₃ 8.00% Twist [°]: 90 CCP-30CF₃ 8.00% V_(10,0,20) [V]: 1.32 CCP-40CF3 3.00% CGU-2-F 10.00% CGU-3-F 10.50% CCG-V-F 1.50% CCGU-3-F 4.00% CBC-33 3.00% BCH-32 2.00% Example M43 BCH-3F•F 10.80% Clearing point [° C.]: +92.0 BCH-5F•F 9.00% Δn [589 nm, 20° C.]: 0.0945 ECCP-30CF₃ 4.50% Δε [1 kHz, 20° C.]: +5.7 ECCP-50CF₃ 4.50% CBC-33F 1.80% CBC-53F 1.80% CBC-55F 1.80% PCH-6F 7.20% PCH-7F 5.40% CCP-20CF₃ 7.20% CCP-30CF₃ 10.80% CCP-40CF₃ 6.20% CCP-50CF₃ 9.90% PCH-5F 9.00% CWCQU-1-F 10.00% Example M44 CC-3-V 16.00% Clearing point [° C.]: 80.6 CCH-35 3.00% Δn [589 nm, 20° C.]: 0.0794 CCP-1F•F•F 10.00% γ₁ [mPa · s, 20° C.]: 117 CCP-2F•F•F 7.00% V_(10,0,20) [V]: 1.22 CCZU-2-F 4.00% CCZU-3-F 15.00% CGZP-2-OT 10.00% CGZP-3-OT 8.00% CGU-3-F 4.00% CWCQU-1-F 6.00% CWCQU-2-F 6.00% CWCQU-3-F 7.00% CCOC-3-3 1.00% CCH-3CF₃ 3.00% Example M45 CC-3-V 16.00% Clearing point [° C.]: 85.0 CCH-35 3.00% Δn [589 nm, 20° C.]: 0.0802 CCP-1F•F•F 10.00% γ₁ [mPa · s, 20° C.]: 121 CCP-3F•F 7.00% V_(10,0,20) [V]: 1.25 CCZU-2-F 4.00% CCZU-3-F 15.00% CGZP-2-OT 10.00% CGZP-3-OT 8.00% CGU-3-F 4.00% CWCQU-1-F 6.00% CWCQU-2-F 6.00% CWCQU-3-F 7.00% CCOC-3-3 1.00% CCH-3CF₃ 3.00% Example M46 CC-3-V 9.00% Clearing point [° C.]: 70.2 CCP-1F•F•F 11.00% Δn [589 nm, 20° C.]: 0.0892 CCP-2F•F•F 5.50% γ₁ [mPa · s, 20° C.]: 143 CCZU-2-F 4.00% V_(10,0,20) [V]: 1.06 CCZU-3-F 15.00% CGZP-2-OT 10.00% CGU-2-F 9.00% PGU-2-F 2.00% PGU-3-F 8.00% CWCQU-1-F 7.00% CWCQU-2-F 7.00% CWCQU-3-F 7.00% CWCQU-5-F 5.50% Example M47 CCP-20CF₃•F 7.00% Clearing point [° C.]: +85.5 CCP-30CF₃•F 7.00% Δn [589 nm, 20° C.]: 0.0757 CCP-50CF₃•F 7.00% V_(10,0,20) [V]: 1.13 CCP-2F•F•F 11.00% CCP-3F•F•F 11.00% CCP-5F•F•F 6.00% CGU-2-F 2.00% CGU-3-F 4.00% CCOC-4-3 2.00% CCOC-3-3 3.00% CWCQU-1-F 4.00% CWCQU-2-F 6.00% CWCQU-3-F 6.00% CDU-2-F 9.00% CDU-3-F 9.00% CDU-5-F 6.00% Example M48 PGU-2-F 7.00% Clearing point [° C.]: +73.0 PGU-3-F 2.00% Δn [589 nm, 20° C.]: 0.0942 CGZP-2-OT 5.00% γ₁ [mPa · s, 20° C.]: 76 CGZP-3-OT 2.00% V_(10,0,20) [V]: 1.59 BCH-3F•F•F 15.00% CCP-1F•F•F 10.00% CCZU-2-F 3.00% CC-3-V1 12.00% CC-5-V 15.00% CCH-35 6.00% PCH-302 10.00% CCP-3F•F 4.00% CWCQU-2-F 4.00% CWCQU-3-F 5.00% Example M49 CCH-35 5.00% S → N [° C.]: <−40.0 CC-3-V1 12.00% Clearing point [° C.]: 83.0 CCP-2F•F•F 10.00% Δn [589 nm, 20° C.]: 0.0946 CCP-20CF₃•F 12.00% CCP-30CF₃•F 2.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 6.00% CCP-50CF₃ 8.00% PUQU-1-F 8.00% PUQU-2-F 6.00% PUQU-3-F 10.00% CCGU-3-F 5.00% Example M50 CCH-35 5.00% S → N [° C.]: <−40.0 CC-3-V1 11.00% Clearing point [° C.]: 84.0 CCP-2F•F•F 10.00% Δn [589 nm, 20° C.]: 0.0934 CCP-3F•F•F 2.00% γ₁ [mPa · s, 20° C.]: 113 CCP-20CF₃•F 12.00% V_(10,0,20) [V]: 1.30 CCP-30CF₃•F 6.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 6.00% CCP-50CF₃ 5.00% PUQU-1-F 8.00% PUQU-2-F 6.00% PUQU-3-F 8.00% CCGU-3-F 5.00% Example M51 CCH-35 5.00% S → N [° C.]: <−40.0 CC-5-V 5.00% Clearing point [° C.]: 84.0 CCP-2F•F•F 10.00% Δn [589 nm, 20° C.]: 0.0940 CCP-3F•F•F 2.00% Δε [1 kHz, 20° C.]: 11.9 CCP-20CF₃•F 12.00% K₃/K₁ [pN, 20° C.]: 1.34 CCP-30CF₃•F 12.00% γ1 [mPa · s, 20° C.]: 127 CCP-20CF₃ 8.00% V_(10,0,20) [V]: 1.24 CCP-30CF₃ 8.00% CCP-40CF₃ 6.00% CCP-50CF₃ 5.00% PUQU-1-F 8.00% PUQU-2-F 6.00% PUQU-3-F 8.00% CCGU-3-F 5.00% Example M52 CCP-1F•F•F 5.00% Clearing point [° C.]: 77.0 CCZU-2-F 4.00% CCZU-3-F 9.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% PUQU-1-F 8.00% PUQU-2-F 6.00% CC-5-V 5.00% CC-3-V1 12.00% CCH-35 5.00% CC-3-V 20.00% CCP-V-1 10.00% Example M53 CCP-1F•F•F 4.00% Clearing point [° C.]: 76.0 CCZU-2-F 4.00% CCZU-3-F 9.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% PUQU-1-F 8.00% PUQU-2-F 6.00% CC-5-V 11.00% CC-3-V1 12.00% CC-3-V 20.00% CCP-V-1 10.00% Example M54 CQU-1-F 8.50% CCZU-3-F 11.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 6.00% CGZP-2-OT 6.00% CGZP-3-OT 3.00% PGU-2-F 5.50% CC-5-V 9.00% CC-3-V1 12.00% CCH-35 5.00% CC-3-V 18.00% Example M55 CQU-1-F 10.00% CQU-2-F 1.50% CCP-2F•F•F 10.00% CCP-20CF₃ 8.00% CCP-30CF₃ 7.00% CCP-40CF₃ 6.00% CCP-20CF₃•F 3.00% CCZU-2-F 4.00% CCZU-3-F 15.00% CCZU-5-F 4.00% CGZP-2-OT 10.00% CGZP-3-OT 8.00% PGU-2-F 3.00% CGU-2-F 6.50% CCGU-3-F 4.00% Example M56 CC-3-V 14.00% CCP-1F•F•F 6.00% CCP-2F•F•F 2.00% CCP-30CF₃ 8.00% CCP-40CF₃ 5.00% CCZU-2-F 4.00% CCZU-3-F 15.00% CCZU-5-F 4.00% CGZP-2-OT 10.00% CGZP-3-OT 8.00% CQU-1-F 7.00% CQU-2-F 7.00% CCOC-4-3 2.50% CCGU-3-F 5.00% CBC-33 2.50% Example M57 CC-3-V1 10.00% CCP-1F•F•F 8.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 5.00% CCP-20CF₃•F 4.00% CCZU-2-F 3.00% CCZU-3-F 15.00% CCZU-5-F 4.00% CGZP-2-OT 10.00% CGZP-3-OT 8.00% CQU-1-F 10.00% CQU-2-F 4.00% CCOC-3-3 1.00% CBC-33 2.00% Example M58 CCH-5CF₃ 4.00% Clearing point [° C.]: 89.0 CCP-20CF₃•F 12.00% Δn [589 nm, 20° C.]: 0.0800 CCP-30CF₃•F 12.00% V_(10,0,20) [V]: 1.18 CCP-50CF₃•F 12.00% CGU-2-F 7.00% CGU-3-F 4.00% CCOC-3-3 2.00% CCOC-4-3 2.00% CCQU-1-F 12.00% CCQU-2-F 10.00% CCQU-3-F 12.00% CCQU-5-F 8.00% CCGU-3-F 3.00% Example M59 PGU-2-F 8.00% S → N [° C.]: <−20.0 PGU-3-F 3.50% Clearing point [° C.]: 75.0 CCP-20CF₃ 8.00% Δn [589 nm, 20° C.]: 0.0918 CCP-30CF₃ 7.00% γ₁ [mPa · s, 20° C.]: 80 CGU-2-F 10.00% V_(10,0,20) [V]: 1.46 CCQU-1-F 7.00% CCQU-2-F 7.00% CCQU-3-F 5.00% CC-3-V1 11.00% CC-5-V 13.00% CCH-35 5.00% BCH-32 3.50% CCG-V-F 12.00% Example M60 CCP-1F•F•F 9.00% S → N [° C.]: <−40.0 CCP-2F•F•F 9.00% Clearing point [° C.]: 82.5 CCP-3F•F•F 3.00% Δn [589 nm, 20° C.]: 0.0918 CCQU-1-F 8.00% γ₁ [mPa · s, 20° C.]: 139 CCQU-2-F 8.00% V_(10,0,20) [V]: 1.20 CCQU-3-F 8.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 6.00% CCP-50CF₃ 3.00% CGU-2-F 10.00% PGU-2-F 7.00% CCP-V-1 4.00% CBC-33 0.50% CCGU-3-F 4.00% CC-3-V1 4.50% Example M61 CCP-2F•F•F 9.00% S → N [° C.]: <−40.0 CCP-3F•F•F 9.00% Clearing point [° C.]: 82.5 CCQU-1-F 9.00% Δn [589 nm, 20° C.]: 0.0917 CCQU-2-F 9.00% γ₁ [mPa · s, 20° C.]: 149 CCQU-3-F 9.00% V_(10,0,20) [V]: 1.28 CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 6.00% CCP-50CF₃ 4.00% CGU-2-F 10.00% CGU-3-F 9.00% BCH-3F•F•F 4.00% CBC-33 1.50% BCH-32 4.50% Example M62 CC-3-V1 5.00% Clearing point [° C.]: 78.0 CCH-35 3.00% γ₁ [mPa · s, 20° C.]: 149 CCP-30CF₃ 5.00% V_(10,0,20) [V]: 1.03 CCZU-2-F 5.00% CCZU-3-F 15.00% CGZP-2-OT 9.00% CGZP-3-OT 7.00% CGU-2-F 10.00% CGU-3-F 10.00% CCQU-1-F 10.00% CCQU-2-F 10.00% CCQU-3-F 11.00% Example M63 CCH-34 5.00% Clearing point [° C.]: 82.0 ECCP-3F•F•F 14.00% Δn [589 nm, 20° C.]: 0.088 PUQU-1-F 7.00% γ₁ [mPa · s, 20° C.]: 135 PUQU-2-F 6.00% V_(10,0,20) [V]: 1.3 PUQU-3-F 6.00% CCP-2F•F 9.00% CCP-3F•F 12.00% CCP-5F•F 12.00% CCP-1F•F•F 3.00% CCP-2F•F•F 9.00% CCP-3F•F•F 8.00% CCP-31 9.00% Example M64 CCH-34 5.00% Clearing point [° C.]: 82.0 CCZU-1-F 3.00% Δn [589 nm, 20° C.]: 0.087 CCZU-2-F 3.00% γ₁ [mPa · s, 20° C.]: 130 CCZU-3-F 8.00% V_(10,0,20) [V]: 1.3 PUQU-1-F 7.00% PUQU-2-F 6.00% PUQU-3-F 6.00% CCP-2F•F 12.00% CCP-3F•F 12.00% CCP-5F•F 9.00% CCP-1F•F•F 3.00% CCP-2F•F•F 9.00% CCP-3F•F•F 8.00% CCP-31 9.00% Example M65 CCH-34 5.00% Clearing point [° C.]: 82.0 CPZU-1-F 2.00% Δn [589 nm, 20° C.]: 0.087 CPZU-2-F 2.00% γ₁ [mPa · s, 20° C.]: 150 CPZU-3-F 2.00% V_(10,0,20) [V]: 1.3 CPZU-5-F 2.00% CCZU-1-F 3.00% CCZU-2-F 3.00% CCZU-3-F 8.00% CCZU-4-F 3.00% BCH-3F•F•F 17.00% CCQU-1-F 7.00% CCQU-2-F 7.00% CCQU-3-F 7.00% CCP-1F•F•F 6.00% CCP-2F•F•F 7.00% CCP-3F•F•F 7.00% CCP-4F•F•F 4.00% CCP-31 8.00% Example M66 PCH-7F 5.00% Clearing point [° C.]: 85.0 BCH-1F•F•F 10.00% Δn [589 nm, 20° C.]: 0.093 BCH-3F•F•F 13.00% γ₁ [mPa · s, 20° C.]: 165 ECCP-3F•F•F 16.00% V_(10,0,20) [V]: 1.6 CCP-1F•F 5.00% CCP-2F•F 5.00% CCP-3F•F 14.00% CCP-4F•F 14.00% CCP-5F•F 14.00% CCP-31 4.00% Example M67 CCH-34 13.00% Clearing point [° C.]: 80.0 CCH-25 10.00% Δn [589 nm, 20° C.]: 0.081 PCH-302 5.00% γ₁ [mPa · s, 20° C.]: 90 PCH-5Cl 18.00% V_(10,0,20) [V]: 1.8 CCP-3F 4.00% CCP-3Cl 8.00% CCP-31 12.00% CCP-1F•F•F 4.00% CCP-3F•F•F 4.00% CPZU-1-F 2.00% CPZU-2-F 2.00% CPZU-3-F 2.00% CPZU-5-F 2.00% CCZU-1-F 4.00% CCZU-3-F 6.00% CCZU-4-F 2.00% CCZU-5-F 2.00% Example M68 CCH-34 12.00% Clearing point [° C.]: 90.0 DCU-3-F 2.00% Δn [589 nm, 20° C.]: 0.093 DCU-4-F 5.00% γ₁ [mPa · s, 20° C.]: 180 DCU-5-F 8.00% V_(10,0,20) [V]: 1.3 CCP-1F•F•F 7.00% CCP-2F•F•F 3.00% CCP-31 10.50% BCH-3F•F•F 20.00% BCH-5F•F•F 6.50% CCZU-1-F 3.00% CCZU-2-F 3.00% CCZU-3-F 9.00% CCZU-5-F 3.00% CCPU-3-F 5.00% CCPU-5-F 3.00% Example M69 CCH-34 4.00% Clearing point [° C.]: 82.0 CPZU-2-F 2.70% Δn [589 nm, 20° C.]: 0.087 CPZU-3-F 2.50% γ₁ [mPa · s, 20° C.]: 185 CPZU-5-F 2.80% V_(10,0,20) [V]: 1.3 CCZU-1-F 3.00% CCZU-2-F 3.00% CCZU-3-F 9.00% CCZU-4-F 3.00% BCH-3F•F•F 14.00% CCP-1F•F•F 8.00% CCP-2F•F•F 6.00% ECCP-3F•F•F 18.00% ECCP-5F•F•F 9.00% CECU-3-F 10.00% CCP-31 5.00% Example M70 BCH-3F•F 10.79% Clearing point [° C.]: 87.3 BCH-5F•F 8.99% Δn [589 nm, 20° C.]: 0.0934 ECCP-30CF₃ 4.49% Δε [1 kHz, 20° C.]: 5.3 ECCP-50CF₃ 4.49% CBC-33F 1.80% CBC-53F 1.80% CBC-55F 1.80% PCH-6F 7.19% PCH-7F 5.39% CCP-20CF₃ 7.19% CCP-30CF₃ 10.79% CCP-40CF₃ 6.29% CCP-50CF₃ 9.89% PCH-5F 8.99% CECG-1-F 10.11% Example M71 BCH-3F•F 10.80% Clearing point [° C.]: 98.6 BCH-5F•F 9.00% Δn [589 nm, 20° C.]: 0.1023 ECCP-30CF₃ 4.50% Δε [1 kHz, 20° C.]: 6.3 ECCP-50CF₃ 4.50% CBC-33F 1.80% CBC-53F 1.80% CBC-55F 1.80% PCH-6F 7.20% PCH-7F 5.40% CCP-20CF₃ 7.20% CCP-30CF₃ 10.80% CCP-40CF₃ 6.30% CCP-50CF₃ 9.90% PCH-5F 9.00% CCGU-1-F 10.00% Example M72 BCH-3F•F 10.80% Clearing point [° C.]: 98.6 BCH-5F•F 9.00% γ₁ [mPa · s, 20° C.]: 157 ECCP-30CF₃ 4.50% ECCP-50CF₃ 4.50% CBC-33F 1.80% CBC-53F 1.80% CBC-55F 1.80% PCH-6F 7.20% PCH-7F 5.40% CCP-20CF₃ 7.20% CCP-30CF₃ 10.80% CCP-40CF₃ 6.30% CCP-50CF₃ 9.90% PCH-5F 9.00% CCGU-1-F 10.00%

The preceding examples can be repeated with similar success by substituting the generically or specifically described reactants and/or operating conditions of this invention for those used in the preceding examples.

From the foregoing description, one skilled in the art can easily ascertain the essential characteristics of this invention and, without departing from the spirit and scope thereof, can make various changes and modifications of the invention to adapt it to various usages and conditions. 

1. A liquid-crystalline medium comprising a mixture of polar compounds of positive or negative dielectric anisotropy, including: one or more compounds of the formula I

in which

are a) a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH₂ groups are optionally replaced by —O— or —S—, b) a 1,4-phenylene radical, in which one or two CH groups are optionally replaced by N, c) a radical selected from the group consisting of piperidine-1,4-diyl, 1,4-bicyclo[2.2.2]octylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl, where the radicals a), b) and c) are optionally monosubstituted or polysubstituted by halogen atoms,

x, y and z are each, independently of one another, 0, 1 or 2, Z¹, Z² and Z³ are each, independently of one another, —CO—O—, —O—CO—, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —CH₂CH₂—, —(CH₂)₄—, —C₂F₄—, —CH₂CF₂—, —CF₂CH₂—, —CF═CF—, —CH═CH—, —C≡C— or a single bond, X is F, Cl, CN, NCS, CF₃, C₂F₅, n-C₃F₇, SF₅, CF₂H, OCF₃, OCF₂H, OCFHCF₃, OCFHCFH₂, OCFHCF₂H, OCF₂CH₃, OCF₂CFH₂, OCF₂CF₂H, OCF₂CF₂CF₂H, OCF₂CF₂CFH₂, OCFHCF₂CF₃, OCFHCF₂CF₂H, OCF₂CF₂CF₃, CF₂CHFCF₃, CF₂CH₂CF₃, OCH₂CF₂CHFCF₃, OCF₂CHFCF₃, OCClFCF₂CF₃, CH₃, C₂H₅ and n-C₃H₇, provided that, when the A⁴ ring is unsubstituted phenyl, X is not CN, CH₃, C₂H₅ or n-C₃H₇, a is 0, 1 or 2, b is 0, 1 or 2, and c is 0, 1 or 2, where a+b+c is from 1 to 3; and additionally comprising one or more compounds of the formula RI to RII, RIV to RVIII, RX to RXII and RXIV:

in which R⁰ is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each having from 2 to 8 carbon atoms, d is 0, 1 or 2, Y¹ is H or F, alkyl and alkyl* are each, independently of one another, a straight-chain or branched alkyl radical having from 2 to 8 carbon atoms, alkenyl and alkenyl* are each, independently of one another, a straight-chain or branched alkenyl radical having from 2 to 8 carbon atoms.
 2. A liquid-crystalline medium according to claim 1, which comprises at least one compound selected from the group consisting of the compounds of the formulae I1, I2, I4 to I16, I20 and I23 to I31:

in which X is as defined in claim 1, alkyl is a straight-chain or branched alkyl radical having 1-8 carbon atoms, and L¹ to L⁶ are each, independently of one another, H or F.
 3. A liquid-crystalline medium according to claim 1, which additionally comprises one or more compounds selected from the group consisting of those of formulae II, III, IV, V, VI, VII, VIII, IX and X:

in which the individual radicals have the following meanings: R⁰ is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each having from 2 to 12 carbon atoms X⁰ is F, Cl, halogenated alkyl, halogenated alkenyl, halogenated alkenyloxy or halogenated alkoxy, each having 1 to 8 carbon atoms, Z⁰ is —CH═CH—, —CH₂O—, —OCH₂—, —(CH₂)₄—, —C₂H₄—, —C₂F₄—, —CF═CF—, —CF₂O—, —OCF₂— or —COO—, Y¹, Y^(2,) Y³ and Y⁴ are each, independently of one another, H or F, and r is 0 or 1; provided that in formula VIII, Z⁰ is not —C₂H₄—.
 4. A liquid-crystalline medium according to claim 3, wherein the proportion of compounds of the formulae I to X in the medium as a whole is at least 50% by weight.
 5. A liquid-crystalline medium according to claim 3, comprising at least one compound wherein X⁰ is F, OCHF₂ or OCF₃, and Y² is H or F.
 6. Electro-optical liquid-crystal display containing a liquid-crystalline medium according to claim
 1. 7. The liquid-crystalline medium of claim 1, wherein the medium exhibits a nematic phase down to −20° C., a clearing point above 80° C., and a dielectric anisotropy, Δ∈, of ≧4.
 8. The liquid-crystalline medium of claim 7, wherein the medium exhibits a TN threshold below 1.5 V.
 9. The liquid-crystalline medium of claim 7, wherein the medium exhibits a flow viscosity, ν₂₀, at 20° C. of <60 mm²·s⁻¹ and a nematic phase range of at least 90° C.
 10. The liquid-crystalline medium of claim 1, wherein the proportion of compounds of formula I in the medium is from 5 to 50% by weight.
 11. The liquid-crystalline medium of claim 1, wherein the medium additionally comprises one or more compounds selected from the group consisting of compounds of the formulae XI or XIII to XVI:

in which R⁰ is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each having from 2 to 8 carbon atoms, Y¹-Y⁴ are, independently, H or F, and X⁰ is F, Cl, halogenated alkyl, halogenated alkenyl, halogenated alkenyloxy or halogenated alkoxy, each having up to 8 carbon atoms.
 12. The liquid-crystalline medium of claim 3, wherein the medium additionally comprises one or more compounds selected from the group consisting of compounds of the formulae XI or XIII to XVI:

in which R⁰ is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each having from 2 to 8 carbon atoms, Y¹-Y⁴ are, independently, H or F, and X⁰ is F, Cl, halogenated alkyl, halogenated alkenyl, halogenated alkenyloxy or halogenated alkoxy, each having up to 8 carbon atoms.
 13. A liquid-crystalline medium comprising a mixture of polar compounds of positive or negative dielectric anisotropy, including: one or more compounds of the formula I

in which

a) a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH₂ groups are optionally replaced by —O— or —S—, b) a 1,4-phenylene radical, in which one or two CH groups are optionally replaced by N, c) a radical selected from the group consisting of piperidine-1,4-diyl, 1,4-bicyclo[2.2.2]octylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl, where the radicals a), b) and c) are optionally monosubstituted or polysubstituted by halogen atoms,

x, y and z are each, independently of one another, 0, 1 or 2, Z¹, Z² and Z³ are each, independently of one another, —CO—O—, —O—CO—, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —CH₂CH₂—, —(CH₂)₄—, —C₂F₄—, —CH₂CF₂—, —CF₂CH₂—, —CF═CF—, —CH═CH—, —C≡C— or a single bond, X is F, Cl, CN, NCS, CF₃, C₂F₅, n-C₃F₇, SF₅, CF₂H, OCF₃, OCF₂H, OCFHCF₃, OCFHCFH₂, OCFHCF₂H, OCF₂CH₃, OCF₂CFH₂, OCF₂CF₂H, OCF₂CF₂CF₂H, OCF₂CF₂CFH₂, OCFHCF₂CF₃, OCFHCF₂CF₂H, OCF₂CF₂CF₃, CF₂CHFCF₃, CF₂CH₂CF₃, OCH₂CF₂CHFCF₃, OCF₂CHFCF₃, OCClFCF₂CF₃, CH₃, C₂H₅ and n-C₃H₇, provided that, when the A⁴ ring is unsubstituted phenyl, X is not CN, CH₃, C₂H₅ or n-C₃H₇, a is 0, 1 or 2, b is 0, 1 or 2, and c is 0, 1 or 2, where a+b+c is from 1 to 3; and additionally comprising one or more compounds selected from the group consisting of those of formulae II, III, IV, V, VI, VII, VIII, IX and X:

in which the individual radicals have the following meanings: R⁰ is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each having from 2 to 12 carbon atoms X⁰ is F, Cl, halogenated alkyl, halogenated alkenyl, halogenated alkenyloxy or halogenated alkoxy, each having 1 to 8 carbon atoms, Z⁰ is —CH═CH—, —CH₂O—, —OCH₂—, —(CH₂)₄—, —C₂H₄—, —C₂F₄—, —CF═CF—, —CF₂O—, —OCF₂— or —COO—, Y¹, Y², Y³ and Y⁴ are each, independently of one another, H or F, and r is 0 or 1; provided that the proportion of compounds of the formulae I to X in the medium as a whole is at least 50% by weight; and provided that in formula VIII, Z⁰ is not —C₂H₄—.
 14. A liquid-crystalline medium according to claim 13, which comprises at least one compound selected from the group consisting of the compounds of the formulae I1, I2, I4 to I16, I20 and I23 to I31:

in which X is as defined in claim 13, alkyl is a straight-chain or branched alkyl radical having 1-8 carbon atoms, and L¹ to L⁶ are each, independently of one another, H or F.
 15. A liquid-crystalline medium according to claim 13, comprising at least one compound wherein X⁰ is F, OCHF₂ or OCF₃, and Y² is H or F.
 16. An electro-optical liquid-crystal display containing a liquid-crystalline medium according to claim
 13. 17. The liquid-crystalline medium of claim 13 wherein the medium exhibits a nematic phase down to −20° C., a clearing point above 80° C., and a dielectric anisotropy, Δ∈, of ≧4.
 18. The liquid-crystalline medium of claim 17, wherein the medium exhibits a TN threshold below 1.5 V.
 19. The liquid-crystalline medium of claim 17, wherein the medium exhibits a flow viscosity, ν₂₀, at 20° C. of <60 mm²·s⁻¹ and a nematic phase range of at least 90° C.
 20. The liquid-crystalline medium of claim 13, wherein the proportion of compounds of formula I in the medium is from 5 to 50% by weight.
 21. The liquid-crystalline medium of claim 13, wherein the medium additionally comprises one or more compounds selected from the group consisting of compounds of the formulae XI or XIII to XVI:

in which R^(o) is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each having from 2 to 8 carbon atoms, Y¹-Y⁴ are, independently, H or F, and X⁰ is F, Cl, halogenated alkyl, halogenated alkenyl, halogenated alkenyloxy or halogenated alkoxy, each having up to 8 carbon atoms.
 22. A liquid-crystalline medium comprising a mixture of polar compounds of positive or negative dielectric anisotropy, including: one or more compounds of the formula I

in which

are a) a 1,4-cyclohexenylene or 1,4-cyclohexylene radical, in which one or two non-adjacent CH₂ groups are optionally replaced by —O— or —S—, b) a 1,4-phenylene radical, in which one or two CH groups are optionally replaced by N, c) a radical selected from the group consisting of piperidine-1,4-diyl, 1,4-bicyclo[2.2.2]octylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl and fluorene-2,7-diyl, where the radicals a), b) and c) are optionally monosubstituted or polysubstituted by halogen atoms,

x, y and z are each, independently of one another, 0, 1 or 2, Z¹, Z² and Z³ are each, independently of one another, —CO—O—, —O—CO—, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —CH₂CH₂—, —(CH₂)₄—, —C₂F₄—, —CH₂CF₂—, —CF₂CH₂—, —CF═CF—, —CH═CH—, —C≡C— or a single bond, X is F, Cl, CN, NCS, CF₃, C₂F₅, n-C₃F₇, SF₅, CF₂H, OCF₃, OCF₂H, OCFHCF₃, OCFHCFH₂, OCFHCF₂H, OCF₂CH₃, OCF₂CFH₂, OCF₂CF₂H, OCF₂CF₂CF₂H, OCF₂CF₂CFH₂, OCFHCF₂CF₃, OCFHCF₂CF₂H, OCF₂CF₂CF₃, CF₂CHFCF₃, CF₂CH₂CF₃, OCH₂CF₂CHFCF₃, OCF₂CHFCF₃, OCClFCF₂CF₃, CH₃, C₂H₅ and n-C₃H₇, a is 0, 1 or 2, b is 0, 1 or 2, and c is 0, 1 or 2, where a+b+c is from 1 to 3; and additionally comprising one or more compounds selected from the group consisting of compounds of the formulae XI or XIII to XVI:

in which R^(o) is n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each having from 2 to 8 carbon atoms, Y¹-Y⁴ are, independently, H or F, and X⁰ is F, Cl, halogenated alkyl, halogenated alkenyl, halogenated alkenyloxy or halogenated alkoxy, each having up to 8 carbon atoms.
 23. A liquid-crystalline medium according to claim 22, which comprises at least one compound selected from the group consisting of the compounds of the formulae I1, I2, I4 to I16, I20 and I23 to I31:

in which X is as defined in claim 22, alkyl is a straight-chain or branched alkyl radical having 1-8 carbon atoms, and L¹ to L⁶ are each, independently of one another, H or F.
 24. An electro-optical liquid-crystal display containing a liquid-crystalline medium according to claim
 22. 25. The liquid-crystalline medium of claim 22, wherein the medium exhibits a nematic phase down to −20° C., a clearing point above 80° C., and a dielectric anisotropy, Δ∈, of ≧4.
 26. The liquid-crystalline medium of claim 25, wherein the medium exhibits a TN threshold below 1.5 V.
 27. The liquid-crystalline medium of claim 25, wherein the medium exhibits a flow viscosity, ν₂₀, at 20° C. of <60 mm²·s⁻¹ and a nematic phase range of at least 90° C.
 28. The liquid-crystalline medium of claim 22, wherein the proportion of compounds of formula I in the medium is from 5 to 50% by weight. 